Systems and methods for preventing sticking and / or repairing high aspect ratio structures

Abstract

A method for processing a high aspect ratio (HAR) structure disposed on a surface of a substrate comprises: a) spin-rinsing the surface of the substrate with a first rinse liquid; b) spinning the first rinse liquid away from the surface of the substrate; and c) directing a gas mixture containing hydrogen fluoride onto the surface of the substrate after dispensing the first rinse liquid.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 62 / 575,705, filed October 23, 2017. The entire contents of the above application are incorporated herein by reference. Technical Field

[0003] The present invention relates to substrate processing, and more particularly, to methods for preventing sticking of high aspect ratio (HAR) structures and / or repairing HAR structures. Background Art

[0004] The background description provided herein is for the purpose of generally presenting the context of the present disclosure. No admission is made, either explicitly or implicitly, that the work of the presently designated inventors to the extent described in this background section and in any aspects of the description that were not identified as prior art at the time the application was filed, is prior art to the present disclosure.

[0005] Substrate processing systems can be used to deposit films or etch, clean, and / or treat substrate surfaces (e.g., semiconductor wafers). In some processes, the substrate may be subjected to wet processing. In these processes, the substrate may be mounted on a spin chuck. As the spin chuck rotates, fluid nozzles may be used to dispense fluids (e.g., liquids or gases) and / or heat may be applied to process the substrate.

[0006] Some substrates include high aspect ratio (HAR) structures. For example, HAR structures may include nanopillars, trenches, or vias. HAR structures have a width (parallel to the substrate surface) that is significantly smaller than the feature depth (perpendicular to the substrate surface). HAR structures with aspect ratios greater than 5:1 are quite common. More advanced processes include structures with even higher aspect ratios. Pattern collapse occurs when one or more of the HAR structures collapses, moves laterally relative to the substrate surface, and / or directly contacts an adjacent HAR structure. Pattern collapse is often encountered during the drying period following a wet cleaning process.

[0007] Several processes have been used to reduce pattern collapse when drying the substrate. For example, supercritical CO2 can be used to dry the substrate. However, supercritical CO2 is relatively expensive and has implementation issues. Layers can be used to modify the substrate surface to prevent sticking. However, surface modification is generally expensive because it requires the use of additional chemicals. Surface modification also results in material loss due to the need to remove the modified layer. Isopropyl alcohol (IPA) can also be used to dry the substrate, which is delivered to the substrate surface at a temperature close to the boiling point of IPA. However, some aspect ratios cannot be dried using boiling IPA without pattern collapse.

[0008] Substrates can also be processed using hydrofluoric acid (HF) vapor etching in vacuum equipment operating at vacuum pressure. However, vacuum equipment is typically expensive and cannot be used to perform wet cleaning. A previous wet cleaning step is often necessary to remove organic or metallic contaminants from the substrate surface.

[0009] Collapsed structure repair can be performed using plasma etching in vacuum equipment. However, the required plasma etching hardware is expensive. Summary of the Invention

[0010] A method for processing a high aspect ratio (HAR) structure disposed on a surface of a substrate comprises: a) spin-rinsing the surface of the substrate with a first rinse liquid; b) spinning the first rinse liquid away from the surface of the substrate; and c) directing a gas mixture containing hydrogen fluoride onto the surface of the substrate after dispensing the first rinse liquid.

[0011] In other features, the hydrogen fluoride is a first reactive component, and the gas mixture further comprises a second reactive component, at least one of the following being present: the second reactive component is a proton acceptor; and / or the second reactive component comprises an OH group.

[0012] In other features, the second reactive component is selected from the group consisting of water vapor, alcohol vapor, ammonia, and amines.

[0013] In other features, c) is performed after b), or c) is performed within 60 seconds after a). The gas mixture further comprises an inert carrier gas and alcohol vapor. The inert carrier gas comprises molecular nitrogen, and the alcohol comprises isopropyl alcohol vapor. The gas mixture is delivered by a nozzle positioned within a range of 1 mm to 40 mm from the surface of the substrate. The gas mixture is delivered from the nozzle at a dispensing velocity within a range of 1 m / s to 50 m / s. The gas mixture is delivered from the nozzle at a flow rate of 1 slm to 20 slm.

[0014] In other features, the cross-sectional area of ​​the orifice of the nozzle is 3 mm 2 Up to 30mm 2 a), b), and c) are performed at a temperature in the range of 20°C to 400°C. a), b), and c) are performed at a temperature in the range of 50°C to 150°C. a), b), and c) are performed while the substrate is maintained at a predetermined pressure in the range of 900 hPa to 1100 hPa. a), b), and c) are performed while the substrate is placed on a spin chuck of the apparatus.

[0015] In other features, the apparatus further comprises: a first liquid distributor connected to a first rinse liquid source; a vapor supply for supplying solvent vapor; and a gas distributor connected to a gas source and the vapor supply to distribute the gas mixture onto the surface of the substrate. The gas distributor comprises a showerhead.

[0016] In other features, the gas distributor includes an arm, a nozzle, and a motor for scanning the arm across the substrate while supplying the gas mixture.

[0017] In other features, a), b), and c) are performed at a temperature greater than 100° C. The gas mixture further comprises ammonia.

[0018] In other features, the first rinse fluid includes an organic, water-miscible solvent.

[0019] In other features, the gas mixture includes hydrogen fluoride in a range of 0.05% to 10% by volume, alcohol in a range of 0.05% to 10% by volume, and inert gas in a range of 80% to 99.9% by volume. The gas mixture includes hydrogen fluoride in a range of 0.5% to 5% by volume, alcohol in a range of 0.5% to 2.5% by volume, and inert gas in a range of 92.5% to 99% by volume. The gas mixture includes hydrogen fluoride in a range of 0.1% to 5% by volume, alcohol in a range of 0.1% to 5% by volume, and inert gas in a range of 90% to 99.8% by volume.

[0020] An apparatus for processing a high aspect ratio (HAR) structure disposed on a surface of a substrate includes a spin chuck for rotating the substrate. As the spin chuck rotates the substrate, a first nozzle rinses the surface of the substrate using a first rinse liquid. After dispensing the first rinse liquid, a second nozzle directs a gas mixture containing hydrogen fluoride onto the surface of the substrate.

[0021] In other features, a first liquid distributor is connected to a first rinse liquid source, a vapor supply supplies a second reactive component, and a gas distributor is connected to a gas source and the vapor supply to distribute the gas mixture onto the surface of the substrate.

[0022] In other features, a mixing manifold mixes the hydrogen fluoride and the second reactive component. An open chamber surrounds the spin chuck. A closed chamber surrounds the spin chuck. A vapor supply supplies solvent vapor. The gas mixture further includes the solvent vapor.

[0023] In other features, the solvent vapor is selected from the group consisting of water vapor and alcohol vapor. After the first rinse liquid is spun off the substrate, the second nozzle directs a gas mixture comprising hydrogen fluoride onto the surface of the substrate. The second nozzle directs the gas mixture comprising hydrogen fluoride onto the surface of the substrate within 60 seconds after dispensing the first rinse liquid.

[0024] In other features, the heater heats the substrate to a temperature in the range of 20° C. to 400° C. The heater heats the substrate to a temperature in the range of 50° C. to 150° C. The substrate is maintained at a predetermined pressure in the range of 900 hPa to 1100 hPa. The heater is configured to heat the substrate to a temperature greater than 100° C., and the gas mixture further comprises ammonia.

[0025] In other features, a controller controls: the rotation of the spin chuck, the dispensing of the first rinse liquid from the first nozzle, and the dispensing of the gas mixture from the second nozzle.

[0026] In other features, the second nozzle is positioned within a range of 1 mm to 40 mm from the surface of the substrate. The gas mixture is delivered from the second nozzle at a dispensing velocity of 1 m / s to 50 m / s. The gas mixture is delivered from the second nozzle at a flow rate of 1 slm to 20 slm. The cross-sectional area of ​​the orifice of the second nozzle is within a range of 3 mm 2 Up to 30mm 2 within the range.

[0027] In other features, the gas mixture comprises hydrogen fluoride in a range of 0.5% to 5% by volume, alcohol in a range of 0.5% to 2.5% by volume, and an inert gas in a range of 92.5% to 99% by volume.

[0028] In other features, the gas mixture comprises an inert gas in a range of 80% to 99.9% by volume, hydrogen fluoride in a range of 0.05% to 10% by volume, and an alcohol in a range of 0.05% to 10% by volume. The gas mixture comprises an inert gas in a range of 90% to 99.8% by volume, hydrogen fluoride in a range of 0.1% to 5% by volume, and an alcohol in a range of 0.1% to 5% by volume.

[0029] Further scope of applicability of the present disclosure will become apparent from the detailed description, claims and drawings.The detailed description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The present disclosure will be more fully understood from the detailed description and accompanying drawings, in which:

[0031] Figures 1A-1C is a side cross-sectional view showing a substrate before and after wet cleaning and drying, and after repair according to the present disclosure;

[0032] Figure 2A is a functional block diagram of an example of a spin chuck disposed in an enclosed chamber for processing a substrate according to the present disclosure;

[0033] Figure 2B for Figure 2A A plan view of a rotary chuck;

[0034] Figure 2C is a functional block diagram of an example of a spin chuck configured in an open chamber for processing a substrate according to the present disclosure;

[0035] Figure 3 is a functional block diagram of another example of a spin chuck for processing a substrate according to the present disclosure;

[0036] Figure 4 A flowchart showing an example of a method for processing a substrate according to the present disclosure is shown below:

[0037] Figure 5 is a flow chart showing another example of a method for processing a substrate according to the present disclosure;

[0038] Figure 6 A functional block diagram showing a wet treatment device and a separate collapse repair device according to the present disclosure is shown below:

[0039] Figure 7 is a functional block diagram of a collapse repair device using an arm and a nozzle according to the present disclosure; and

[0040] Figure 8 It is a functional block diagram of a collapse repair device using a nozzle according to the present disclosure.

[0041] Among the drawings, reference numerals may be repeated to identify similar and / or identical elements. DETAILED DESCRIPTION

[0042] Systems and methods according to the present disclosure relate to wet processing and dry etching of substrates containing high aspect ratio (HAR) structures. After the substrate has been processed, the wet processing and dry etching can be performed in a wet cleaning tool at or near atmospheric pressure. The combination of wet processing and dry etching in a single hardware device provides a less expensive alternative to other drying processes and adds little or no processing time. Alternatively, the wet processing can be completed in the wet processing tool, while the repair process can be performed in a separate repair tool.

[0043] In some examples, after exposure to a rinse fluid such as isopropyl alcohol (IPA), a gas mixture is dispensed onto the substrate surface. The gas mixture includes hydrofluoric acid (HF) gas. In some examples, the gas mixture may also include a second reactive component (e.g., solvent vapor or a proton acceptor, or a component having OH groups) and / or a carrier gas.

[0044] In some examples, the carrier gas comprises an inert gas such as molecular nitrogen (N2). However, other inert gases may be used. In some examples, the second reaction component comprises water or an alcohol (methanol, IPA, or other alcohols). Other alcohols may be used. For example, an alcohol having 1 to 4 carbon (C) atoms may be used. For example, 2-propanol (IPA) may be used. In some examples, the gas mixing method comprises mixing N2 with IPA and then adding pure HF gas to the IPA / N2 mixture.

[0045] For example, an adsorption layer of the solvent is formed, and HF2 is generated. SiO2 reacts with HF2 and forms SiF4, which causes vaporization (etching) of the SiO2 layer. In some examples, the gas mixture includes HF in a range of 0.5% to 5% by volume, an alcohol in a range of 0.5% to 2.5% by volume, and an inert gas in a range of 92.5% to 99% by volume.

[0046] In some examples, the gas mixture is produced by flowing N2 gas as a carrier gas through concentrated aqueous HF, wherein the HF concentration is in the range of 45% to 55% by volume (e.g., 49% by volume). In other examples, the gas mixture is prepared by mixing an inert gas (e.g., molecular nitrogen) with an alcohol and then adding pure HF to the inert gas and alcohol mixture.

[0047] In other examples, the gas mixture includes an inert gas in a range of 80% to 99.9% by volume, HF in a range of 0.05% to 10% by volume, and alcohol in a range of 0.05% to 10% by volume. In other examples, the gas mixture includes an inert gas in a range of 90% to 99.8% by volume, HF in a range of 0.1% to 5% by volume, and alcohol in a range of 0.1% to 5% by volume.

[0048] In other examples, ammonia (NH3) or any amine (e.g., ethylamine, ethylenediamine, pyrrolidine) is optionally added to the gas mixture when the processing temperature is greater than 100° C. The addition of NH3 is particularly effective at temperatures above 100° C., where the formation of NH4F is suppressed (because it is above the sublimation temperature) and volatile (NH4)2SiF4 is formed.

[0049] Alternatively, the treatment may be applied to the substrate after the rinse solution has been spun out of the substrate and the substrate is relatively dry. In some examples, the treatment may include exposing in the presence of the rinse solution and then applying the treatment again after the rinse solution has been spun out and dried. The treatment may be repeated one or more times.

[0050] In some examples, the process is performed at or near atmospheric pressure. For example, the substrate surface can be maintained at a pressure in the range of 900 to 1100 hectopascals (hPa) during the process. In some examples, the gas mixture is delivered to the substrate using a nozzle that scans across the substrate surface. Alternatively, the gas mixture can be delivered to the substrate using a showerhead positioned above the substrate surface. In addition, vapors that can potentially enhance the process, such as water or ammonia (NH3) vapor (gas), or amines, can be supplied.

[0051] In some examples, the process is performed at a predetermined temperature in the range of 20° C. to 400° C. In other examples, the process is performed at a predetermined temperature in the range of 50° C. to 150° C. The partial pressures of HF and solvent vapors can vary between 1 mTorr and up to their respective saturated vapor pressures at the particular process temperature.

[0052] Reaction vapor (for example the combination of HF / solvent vapor) is added drying process and the result through improvement is provided with respect to other IPA drying processes.In some examples, use has the substrate heater of radial heating and / or the nozzle that can scan above substrate, to carry out the controllability of vapor etching.Except reducing hardware and chemical cost, method described herein makes the yield of technology improve.

[0053] Now refer to Figures 1A-1C , showing the processing of the substrate. Figure 1A , a substrate 10 is shown prior to wet processing and drying. The substrate 10 includes high aspect ratio (HAR) structures 12-1, 12-2, 12-3, and 12-4 (collectively, HAR structures 12) defined on one or more underlying layers 14. For example, the HAR structures 12 include pillars, vias, trenches, and / or other features. Figure 1A The substrate 10 in the embodiment is subjected to wet treatment and drying.

[0054] exist Figure 1B , the substrate 10 is shown after wet processing and drying. The HAR structures 12-2 and 12-3 are partially collapsed and tilted relative to each other. In some examples, a bridging oxide 20 is formed between the HAR structures 12-2 and 12-3. Examples of bridging oxides that can be formed include silicon oxide (SiO x ), silicon oxynitride (SiO x N y), titanium oxide (TiO x ) etc. Figure 1C , the substrate 10 is shown after being processed using the methods described herein to remove the bridging oxide 20 and repair the collapsed HAR structures 12 - 2 and 12 - 3 .

[0055] Now refer to Figure 2A , shows an example of a spin chuck 50 for wet processing and repairing substrates. Spin chuck 50 includes a chamber 52 that houses spin chuck 56. A substrate 58 is disposed on a surface of spin chuck 50. Spin chuck 50 rotates substrate 58 while dispensing liquid onto and / or spinning liquid out of substrate 58. Any suitable mechanism can be used to attach substrate 58 to spin chuck 50. For example, clamping pins 59 can be used to attach substrate 58 to spin chuck 50. Suitable examples of clamping pins are shown and described in commonly assigned U.S. patent application Ser. No. 15 / 232,594 (Attorney Docket No. 3877-1US) entitled "Method and Apparatus for Processing Wafer-Shaped Articles," which is incorporated herein by reference in its entirety.

[0056] In some examples, the surface 60 of the rotary chuck 56 is transparent, and the heater 61 is disposed below the surface 60. In some examples, the heater 61 comprises a plurality of light emitting diodes (LEDs) disposed in one or more radial zones to enable radial heating of the substrate 58. In some examples, the heater 61 is operable to provide a moving heat wave that moves from a central position of the substrate outward to its radial outer edge. In some examples, the rotary chuck 56 rotates while the heater 61 is stationary. A suitable example of a rotary chuck for performing radial heating of a substrate is shown and described in U.S. patent application Ser. No. 15 / 232,594.

[0057] In some examples, spin chuck 56 is rotated by motor 62 via drive shaft 63, as shown. In other examples, motor 62 includes a rotor and a stator, and the rotor is magnetically driven without physical contact. Suitable examples are shown in commonly assigned U.S. Patent No. 6,485,531, which is incorporated herein by reference in its entirety. Rinse liquid is delivered by arm 64 and nozzle 66, which are scanned across substrate 58 by motor 70. Valve 72 selectively supplies rinse liquid from liquid supply 74 to arm 64.

[0058] The other arm 84 (shown in Figure 2AIn some examples, the outlet of the gas nozzle 86 is positioned at a predetermined distance from the surface of the substrate 58. In some examples, the predetermined distance is in the range of 1 mm to 40 mm. In some examples, the predetermined distance is in the range of 2 mm to 2 cm. In some examples, the gas mixture is delivered at a predetermined speed in the range of 1 to 50 m / s. In some examples, the gas mixture is delivered at a predetermined flow rate in the range of 1 to 20 standard liters per minute (slm). In some examples, the cross-sectional area of ​​the orifice of the nozzle 86 is in the range of 3 to 30 mm. 2 within the range.

[0059] Motor 90 can be used to scan nozzle 86 across substrate 58, and valve 92 can be used to selectively supply a gas mixture. Gas delivery system 100 includes a vapor supply 102 and a valve 104. In some examples, vapor supply 102 includes a heated liquid ampoule, a bubbler, or other vaporizer. Gas delivery system 100 also includes one or more gas supplies 112-1, 112-2, ..., and 112-N (collectively referred to as gas supplies 112) and valves 114-1, 114-2, ..., and 114-N (collectively referred to as valves 114). An optional manifold 110 can be used to allow gas and vapor to mix before being delivered via optional valve 92. In some examples, a mass flow controller (not shown) is provided to more precisely control the gas and / or solvent vapor. Controller 130 controls the valves, motor, and gas delivery system 100.

[0060] exist Figure 2B , arms 64 and 84 are shown in plan view. Arm 64 is shown in a dispensing position above substrate 58, while arm 84 is shown in an inactive position. Arm 64 dispenses a rinse liquid onto the substrate, which is then rotated out. After dispensing the rinse liquid, arm 64 is moved to the inactive position, while arm 84 dispenses a gas mixture, as will be described further below.

[0061] Now refer to Figure 2C, a spin chuck with an open chamber can also be used. Additional details of an open chamber spin chuck are shown in commonly assigned U.S. Patent No. 9,484,229, which is hereby incorporated by reference in its entirety. The spin chuck 150 is disposed in a chamber 151, which is open at its top. The bottom of the chamber 151 can be open or closed. The chamber 151 defines one or more exhaust channels 152. In some examples, the one or more exhaust channels 152 are positioned in a plane containing the substrate 58, point radially outward, and are connected to a vacuum source. In some examples, the vacuum source includes a valve 153 and a pump 154 ​​in fluid communication with the one or more exhaust channels 152.

[0062] In some examples, the spin chuck 150 includes a plurality of clamping pins 155 disposed thereon and a transparent plate 156 disposed below the substrate 58. A heater 157 (e.g., a printed circuit board containing light emitting diodes (LEDs)) can be disposed below the transparent plate 156 to heat the substrate 58. In some examples, the heater 157 generates a moving heat wave that is used during cleaning and / or repair. The moving heat wave moves outward from a central position of the substrate to its radially outer edge. In some examples, the heater 157 is stationary while the spin chuck 150 rotates. A suitable example of a spin chuck that performs radial heating of a substrate is shown and described in U.S. patent application Ser. No. 15 / 232,594. In some examples, a fan 158 supplies an air flow 159 to the top surface of the chamber 151 during processing.

[0063] Now refer to Figure 3 , shows another example of a spin chuck for processing a substrate. Instead of using arm 84 and nozzle 86, the gas mixture is distributed using showerhead 136 positioned above the surface of substrate 58. Other suitable examples of delivering gas to a spin chuck through a showerhead are shown and described in commonly assigned U.S. Patent No. 8,926,788, and commonly assigned U.S. Patent Publication Nos. US2012 / 0131815 and US2014 / 0026926, which are hereby incorporated by reference in their entireties.

[0064] In some examples, the showerhead 136 comprises a plate having a plurality of perforations. A gas mixture is delivered to the gas plenum 134 via the gas delivery system 100 and the valve 92. The gas mixture flows into the gas plenum 134, through the showerhead 136, and into the chamber 52 to expose the substrate 58. In some examples, when repairing or preventing collapse, the vertical position of the showerhead 136 and the gas plenum 134 is adjusted closer to the substrate by one or more motors 170 before delivering the gas mixture.

[0065] Now refer to Figure 4-5 , shows an example of a method for processing a substrate. Figure 4 In FIG, a method 180 for processing a substrate is shown. Figure 4 At 184, a substrate is placed on a spin chuck. At 188, the spin chuck is rotated. At 192, a rinse liquid is dispensed onto the substrate. At 194, the rinse liquid is spun out.

[0066] After the predetermined period (at 198), the gas mixture is supplied at 202. In other examples, the gas mixture may be applied in an overlapping manner during 194. The substrate may or may not be rotating while the gas mixture is being applied.

[0067] In some examples, the predetermined time period is in the range of 0 to 60 seconds. In some examples, the gas mixture is supplied before the end of the flushing step 192. In some examples, the gas mixture includes hydrofluoric acid (HF) gas and a carrier gas. The gas mixture is supplied for the predetermined time period to prevent collapse and / or repair the HAR structure by removing bridging oxide.

[0068] exist Figure 5 , a method 210 for processing a substrate is shown. Steps 184 to 198 are similar to the steps described above. After a predetermined period of time (198), a gas mixture is supplied at 214. The gas mixture comprises hydrofluoric acid (HF) gas, a carrier gas, and at least one of solvent vapor and ammonia gas. The gas mixture is supplied for a predetermined period of time to prevent collapse and / or repair the HAR structure. Without being limited to a particular theory, the collapse prevention and / or repair of the HAR structure is performed by directing HF gas onto the substrate to remove stiction forces (e.g., van der Waals forces, hydrogen bonds, and covalent oxide bridges).

[0069] In one example, the repair process according to the present disclosure was tested on a substrate having HAR structures comprising nanopillars (silicon (Si) cylinders with a diameter of 30 nm, a pitch of 90 nm, and a height of 600 nm). Using the repair process according to the present disclosure, the process reduced the collapse percentage from nearly 90% to less than 10%.

[0070] Now refer to Figure 6-8 , wet treatment and collapse repair can be performed in separate units. Figure 6 In the embodiment of the present invention, system 288 includes a wet processing device 290 for performing a wet processing step. After the wet processing in wet processing device 290, the substrate is moved to collapse repair device 300. In some examples, the wet processing step includes wet cleaning. In some examples, the wet processing step is performed by a spin chuck.

[0071] exist Figure 7, a collapse repair apparatus 300 is shown. The collapse repair apparatus 300 includes a chamber 310 and a substrate support 312 for supporting a substrate 314. The substrate support 312 includes a heater 320 (e.g., a resistive heater) and / or cooling channels to control the temperature of the substrate 314 during processing. A controller 130 controls the motor 90, valve 92, and gas delivery system 100 to perform collapse repair. Because the collapse repair apparatus 300 does not perform wet cleaning, the nozzle and spin chuck associated with wet processing apparatuses are omitted, simplifying the collapse repair apparatus 300.

[0072] exist Figure 8 , another example of a collapse repair device 350 is shown. Figure 7 The nozzle 86, arm 84, and motor 90 of the collapse repair device in FIG. 3 are replaced by a showerhead 360 positioned above the surface of substrate 314. In some examples, showerhead 360 comprises a plate having a plurality of perforations. A gas mixture is delivered to gas plenum 362 via gas delivery system 100 and / or valve 92. The gas mixture flows into gas plenum 362 and passes through showerhead 360, exposing substrate 314.

[0073] The foregoing description is merely illustrative in nature and is in no way intended to limit the present disclosure, its application or use. The broad teachings of the present disclosure can be implemented in various forms. Therefore, although the present disclosure includes specific examples, the true scope of the present disclosure should not be so limited, because other modifications will become apparent when studying the drawings, description and appended claims. It should be understood that one or more steps in the method can be performed in a different order (or simultaneously) without changing the principles of the present disclosure. In addition, although each embodiment is described above as having certain features, any one or more of those features described with respect to any embodiment of the present disclosure can be implemented in the features of any other embodiment and / or combined with the features of any other embodiment, even if the combination is not explicitly described. In other words, the described embodiments are not mutually exclusive, and the permutation of one or more embodiments to each other remains within the scope of the present disclosure.

[0074] Various terms are used to describe the spatial and functional relationships between elements (e.g., between modules, between circuit elements, between semiconductor layers, etc.), including "connected," "engaged," "coupled," "adjacent," "next to," "on top of," "above," "below," and "disposed." Unless the relationship between a first and a second element is explicitly described as "direct," when such a relationship is described in the above disclosure, the relationship can be a direct relationship, in which there are no other intervening elements between the first and second elements, but can also be an indirect relationship, in which there are one or more intervening elements (spatially or functionally) between the first and second elements. As used herein, the phrase "at least one of A, B, and C" should be construed to mean a logical (A or B or C), using a non-exclusive logical OR, and should not be construed to mean "at least one of A, at least one of B, and at least one of C."

Claims

1. A method for processing a high aspect ratio structure provided on a surface of a substrate, the method comprising: a) performing a rotational rinse on the surface of the substrate using a first rinse liquid; b) rotating the first rinse liquid away from the surface of the substrate; and c) after dispensing the first rinse liquid, directing a gas mixture containing hydrogen fluoride onto the surface of the substrate to eliminate viscous forces of at least one of van der Waals forces, hydrogen bonds, and covalent oxide bridges acting on the high aspect ratio structure and repair collapse of the high aspect ratio structure, in, a), b) and c) are performed when the substrate is maintained at a predetermined pressure in a range from 900 hPa to 1100 hPa in a single chamber. Furthermore, in c), when the treatment temperature exceeds 100° C., ammonia is added to the gas mixture containing hydrogen fluoride to suppress the formation of ammonium fluoride.

2. The method of claim 1, wherein the hydrogen fluoride is a first reactive component and the gas mixture further comprises a second reactive component.

3. The method according to claim 2, wherein: At least one of the following exists: The second reaction component is a proton acceptor: and / or The second reactive component comprises an OH group.

4. The method of claim 3, wherein the second reactive component is selected from the group consisting of water vapor, alcohol vapor, ammonia, and amines.

5. The method according to claim 2, wherein: Perform c) after b).

6. The method according to claim 2, wherein: Perform c) within 60 seconds of a).

7. The method of claim 1, wherein the gas mixture further comprises an alcohol and an inert carrier gas.

8. The method of claim 7, wherein the inert carrier gas comprises molecular nitrogen and the alcohol comprises isopropyl alcohol.

9. The method of claim 1, wherein the gas mixture is delivered by a nozzle positioned in a range of 1 mm to 40 mm from the surface of the substrate.

10. The method of claim 1, wherein the gas mixture is delivered from the nozzle at a dispensing velocity in the range of 1 m / s to 50 m / s.

11. The method of claim 1, wherein the gas mixture is delivered from the nozzle at a flow rate of 1 slm to 20 slm.

12. The method according to claim 1, wherein the cross-sectional area of ​​the orifice of the nozzle delivering the gas mixture is 3 mm 2 Up to 30mm 2 within the range.

13. The method of claim 1, wherein a), b) and c) are performed at a temperature in the range of 20°C to 400°C.

14. The method of claim 1, wherein a), b) and c) are performed at a temperature in the range of 50°C to 150°C.

15. The method according to claim 1, wherein a), b) and c) are performed with the substrate disposed on a spin chuck of the apparatus.

16. The method of claim 15, wherein the device further comprises: a first liquid distributor connected to a first flushing liquid source; a vapor supply portion for supplying solvent vapor; and A gas distributor is connected to a gas source and the vapor supply to distribute the gas mixture onto the surface of the substrate. The method of claim 16 , wherein the gas distributor comprises a showerhead.

18. The method of claim 16, wherein the gas distributor comprises: Arm; nozzle; and A motor is provided for causing the arm to scan across the substrate while supplying the gas mixture.

19. The method of claim 1, wherein: Wherein a), b) and c) are performed at a temperature greater than 100°C.

20. The method according to claim 1, wherein The first rinse fluid includes an organic, water-miscible solvent.

21. The method according to claim 1, wherein The gas mixture includes the hydrogen fluoride in an amount ranging from 0.05% to 10% by volume, the alcohol in an amount ranging from 0.05% to 10% by volume, and the inert gas in an amount ranging from 80% to 99.9% by volume.

22. The method according to claim 1, wherein The gas mixture includes 0.5 to 5 volume % of the hydrogen fluoride, 0.5 to 2.5 volume % of the alcohol, and 92.5 to 99 volume % of the inert gas.

23. The method according to claim 1, wherein The gas mixture includes the hydrogen fluoride in an amount ranging from 0.1% to 5% by volume, the alcohol in an amount ranging from 0.1% to 5% by volume, and the inert gas in an amount ranging from 90% to 99.8% by volume.

24. A chamber for processing high aspect ratio structures disposed on a surface of a substrate, comprising: a spin chuck disposed in the chamber and configured to rotate the substrate; a first nozzle for rinsing the surface of the substrate in the chamber with a first rinsing liquid at a predetermined pressure ranging from 900 hPa to 1100 hPa while the spin chuck rotates the substrate; as well as a second nozzle for directing a gas mixture containing hydrogen fluoride onto the surface of the substrate in the chamber at the predetermined pressure in the range of 900 hPa to 1100 hPa after dispensing the first rinse liquid, thereby eliminating viscous forces of at least one of van der Waals forces, hydrogen bonds, and covalent oxide bridges acting on the high aspect ratio structure; wherein ammonia is added to the gas mixture containing hydrogen fluoride to suppress the formation of ammonium fluoride when the processing temperature exceeds 100°C.

25. The chamber of claim 24, further comprising: a first liquid distributor connected to a first flushing liquid source; a steam supply portion for supplying a second reaction component; as well as A gas distributor is connected to a gas source and the vapor supply to distribute the gas mixture onto the surface of the substrate.

26. The chamber of claim 25, further comprising a mixing manifold for mixing the hydrogen fluoride and the second reactive component.

27. The chamber of claim 24, further comprising an open chamber surrounding the spin chuck.

28. The chamber of claim 24, further comprising an enclosed chamber surrounding the spin chuck.

29. The chamber of claim 24, further comprising a vapor supply to supply solvent vapor, wherein the gas mixture further comprises the solvent vapor.

30. The chamber of claim 29, wherein The solvent vapor is selected from the group consisting of water vapor and alcohol vapor.

31. The chamber of claim 24, wherein After spinning the first rinse liquid out of the substrate, the second nozzle directs a gas mixture containing hydrogen fluoride onto the surface of the substrate.

32. The chamber of claim 24, wherein The second nozzle directs the gas mixture comprising hydrogen fluoride onto the surface of the substrate within 60 seconds after dispensing the first rinse liquid.

33. The chamber of claim 24, further comprising a heater for heating the substrate to a temperature in the range of 20°C to 400°C.

34. The chamber of claim 24, further comprising a heater for heating the substrate to a temperature in the range of 50°C to 150°C.

35. The chamber of claim 24, further comprising a heater for heating the substrate to a temperature greater than 100°C.

36. The chamber of claim 24, further comprising a controller for controlling the rotation of the spin chuck, the dispensing of the first rinse liquid from the first nozzle, and the dispensing of the gas mixture from the second nozzle.

37. The chamber of claim 24, wherein The second nozzle is positioned within a range of 1 mm to 40 mm from the surface of the substrate.

38. The chamber of claim 24, wherein The gas mixture is delivered from the second nozzle at a dispensing velocity of 1 m / s to 50 m / s.

39. The chamber of claim 24, wherein The gas mixture is delivered from the second nozzle at a flow rate of 1 slm to 20 slm.

40. The chamber of claim 24, wherein The cross-sectional area of ​​the orifice of the second nozzle is 3 mm 2 Up to 30mm 2 within the range.

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